JP2016060202A - Polyolefin-based fiber-reinforced resin laminate sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin-based fiber-reinforced resin laminate sheet which has a stereoscopic effect and decorative appearance and can integrate components by injection molding; and a method for producing the same.SOLUTION: A polyolefin-based fiber-reinforced resin laminate sheet (8) includes textile layers (3a and 3b) laminated on both surfaces of a core layer (1) through adhesive layers (2a and 2b). The core layer (1) is a polypropylene-based resin containing a coloring agent. The textile layers (3a and 3b) are formed of a thread containing a composite fiber which contains polypropylene as a first component and contains a polyolefin component having a lower melting point than that of the first component as a second component. The adhesive layers (2a and 2b) are heat-fusible polyolefin-based films. A cover layer (7) is laminated on one surface of the textile layers (3a and 3b).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyolefin-based fiber reinforced resin laminate sheet having a three-dimensional effect and capable of integrating parts by injection molding and a method for producing the same.

  Conventionally, a laminate in which a plurality of reinforcing fiber fabrics such as carbon fibers and aramid fibers are laminated or integrated with a foam sheet is known. Patent Document 1 proposes a laminated sheet in which a carbon fiber fabric layer is integrated on the surface of a core layer made of a foam. In addition, a laminate in which a carbon fiber fabric and an aramid fiber fabric are integrated with a polycarbonate film as an adhesive layer has also been proposed (Patent Document 2). Furthermore, it has also been proposed to laminate unidirectional fiber bodies on both surfaces of a hollow core (Patent Document 3). These laminates are advantageous in that they are lightweight and have high bending strength.

JP 2012-096482 A Japanese Patent Laid-Open No. 5-117411 JP 2009-000933 A

  However, the conventional laminate uses an expensive material such as carbon fiber, aramid fiber, or hollow core, and has a problem of high cost.

  In order to solve the above-mentioned conventional problems, the present invention has no delamination, is lightweight, has a high physical strength against bending, is inexpensive, has a three-dimensional effect and a beautiful appearance, and is an integral part by injection molding. Provided is a polyolefin-based fiber reinforced resin laminated sheet and a method for producing the same.

  The polyolefin-based fiber reinforced resin laminate sheet of the present invention is a polyolefin-based fiber reinforced resin laminate sheet comprising a fabric layer laminated on both surfaces of the core layer via an adhesive layer, wherein the core layer includes a polypropylene containing a colorant. The woven fabric layer is composed of a yarn including a composite fiber in which the first component is polypropylene and the second component is a polyolefin component having a melting point lower than that of the first component, and the adhesive layer is a heat fusion polyolefin type It is a film, The cover layer is laminated | stacked on one surface of the said fabric layer, It is characterized by the above-mentioned.

  The method for producing a polyolefin-based fiber reinforced resin laminate sheet of the present invention is a method for producing the above-mentioned polyolefin-based fiber reinforced resin laminate sheet, which is a fabric for a cover layer sheet and a core sheet through adhesive films on both surfaces. Is placed, heated and pressurized, and then cooled.

  In the present invention, since the core layer, the adhesive layer, the fabric layer, and the cover layer constituting the fiber reinforced resin laminated sheet are all olefin-based resins, the cost is reduced, and at the same time, there is no delamination, light weight, bending Therefore, it is possible to provide a laminated sheet having a high three-dimensional effect and a beautiful appearance. Further, this laminated sheet is thermoplastic and is suitable for vacuum forming, press forming, bending forming utilizing thermal deformation, and the like. In addition, since the fabric layer is bonded to the core layer via a heat-sealable polyolefin film, there is no shrinkage of the fibers constituting the fabric even if it is heated and formed later, and the beautiful woven pattern of the fabric is a laminated sheet as it is It can be set as a molded body appearing on the surface. Furthermore, since this laminated sheet has the fabric layer as the outermost layer, it is possible to provide a laminated sheet that can be integrated into the fabric layer by injection molding. In addition, since the core layer is colored, light transmission from the outside can be prevented.

FIG. 1 is a schematic cross-sectional view of a laminated sheet according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a laminated sheet manufacturing apparatus in one embodiment of the present invention. FIG. 3 is a schematic perspective view of a molded body obtained by vacuum forming the laminated sheet of one embodiment of the present invention.

  The fiber reinforced resin laminate sheet of the present invention includes a fiber reinforced layer in which a fabric layer is bonded to both surfaces of a core layer via an adhesive layer. The core layer is a polypropylene resin containing a colorant. Since the core layer is colored, light transmission from the outside can be prevented. When the core layer is 100% by weight, the amount of the colorant added is not particularly limited, but is about 0.01 to 5.0% by weight. As the color tone of the colorant, any color such as white can be selected. When the colorant is white, for example, titanium oxide powder is used. The coloring of the core layer is more preferably the same color as the fabric layer. If the fabric layer looks white, the core layer can also be colored white so that the fabric layer can be expressed more beautifully.

  The polypropylene resin in the core layer is preferably a resin mainly composed of polypropylene or propylene. This core layer is laminated in the form of a sheet or film. A polypropylene sheet or a resin mainly composed of propylene has the advantages of practically satisfying physical properties and low cost. In the above, the main component means that the propylene unit is 50 mol% or more when the entire resin component is 100 mol%. The fiber reinforced resin laminated sheet may be simply referred to as a laminated sheet.

  When polypropylene is used as the core layer, homopolymer type polypropylene (HPP) is preferred. HPP has a melting point of about 160 ° C. and high hardness, and is less susceptible to defects such as sink marks and wrinkles during subsequent molding and component mounting.

  The core layer may be a propylene-ethylene random copolymer (RPP). RPP is a random copolymer containing 50 mol% or more of propylene units and 50 mol% or less of ethylene units, and has a melting point of 135 to 150 ° C. and is generally commercially available. RPP has an advantage of excellent heat-fusibility. A preferable thickness of the core layer is 0.1 to 2 mm, and more preferably 0.2 to 1.5 mm.

  The core layer is preferably a non-foamed polypropylene sheet. The non-foamed polypropylene-based sheet does not collapse the core layer even by press molding, and vacuum molding, bending processing using thermal deformation, and the like can be easily performed.

  The composite fiber constituting the fabric layer is preferably a core-sheath composite fiber in which the first component is a core and the second component is a sheath. Specifically, the woven fabric layer is preferably composed of yarn containing core-sheath composite fibers in which the core component is polypropylene and the sheath component is a polyolefin component having a melting point lower than that of the core component. By using a low-melting-point polyolefin-based component as the sheath component, it becomes easy to heat-bond. Furthermore, by using a heat-sealable polyolefin film as the adhesive layer, the core layer and the fabric layer can be bonded with heat and pressure, and lamination and integration are easy.

  The core component of the core-sheath composite fiber is preferably a homopolymer polypropylene, and the sheath component is preferably a propylene-ethylene random copolymer (RPP), a blend of polypropylene and polyethylene, or a polyethylene resin. This further facilitates heat bonding.

  The heat-sealable polyolefin film is preferably low density polyethylene (LLDPE) or RPP. LLDPE and RPP are excellent in heat processability, adhesiveness and transparency.

The woven fabric may be a woven fabric having any structure such as plain weave, twill weave (oblique fabric), satin weave, and other changed weaves. The yarn constituting the woven fabric is preferably a multifilament or monofilament having a single fiber fineness of 1 to 10 deci tex and a total fineness of 1000 to 3000 deci tex. The weight (unit weight) per unit area of the woven fabric is preferably in the range of 50 to 500 g / m ² .

  In the laminated sheet of the present invention, a cover layer is laminated and integrated on one surface layer of the fiber reinforced layer, preferably via an adhesive layer. This cover layer is preferably transparent so that the fabric layer can be seen from the outside. When the fabric layer is seen from the outside, it looks high-strength and can maintain a beautiful appearance. In this sense, it can also be called an optical cover layer. The cover layer is preferably composed of a polypropylene resin sheet transparent layer, a colored layer, and a polypropylene resin sheet protective layer. Among such transparent cover layers, the polypropylene resin sheet transparent layer is preferably a relatively thick sheet, for example, having a thickness of 100 to 300 μm, preferably 150 to 250 μm. If it does in this way, a three-dimensional feeling and a thickness feeling can be exhibited.

  The polypropylene resin sheet transparent layer is preferably a blend or polymer alloy of homopolymer type polypropylene (HPP) and propylene-ethylene random copolymer (RPP). When the transparent layer is 100% by weight, the homopolymer type polypropylene (HPP) and the propylene-ethylene random copolymer (RPP) are preferably in the range of HPP: RPP = 50: 50 to 90:10, more preferably HPP. : RPP = 60: 40-80: 20. If it is the said range, the high transparency by the amorphous of a random type polypropylene (RPP) and the abrasion resistance of a homopolymer type polypropylene (HPP) can coexist.

  It is preferable to form a colored layer on the transparent layer. The colored layer is for external appearance, and it is preferable to apply a thin colored paint in order to maintain transparency. The preferred thickness of the colored layer is 0.1 to 2 μm, more preferably 0.2 to 1 μm. An arbitrary color tone can be selected for the colored layer. It is preferable to provide a protective layer for the propylene-based resin sheet on the colored layer. This protective layer is preferably a biaxially stretched polypropylene resin sheet. A biaxially stretched polypropylene resin sheet is preferred because of its high wear resistance. The preferred thickness of the biaxially oriented polypropylene resin sheet is 5 to 50 μm, more preferably 10 to 40 μm.

  According to the present invention, a transparent layer of a polypropylene resin sheet, a colored layer, and a protective layer of a polypropylene resin sheet are laminated on one surface layer of a fiber reinforced layer, preferably via an adhesive layer, so that a transparent layer having a thickness from the outside is formed. The fabric layer can be seen through and a beautiful and beautiful woven pattern of the fabric appears on the surface of the laminated sheet as it is. The other surface layer is a fabric layer, and when the parts by injection molding are integrated with this fabric layer, the surface of the fabric is uneven, so the injection molded parts are easy to integrate, and the fabric layer is deformed by heating. There are no defects such as sink marks and wrinkles. As a result, a laminated sheet having an excellent appearance such as gloss and coloring can be obtained.

Furthermore, the laminated sheet of this invention can also add a polyaxial fiber sheet between a core layer and a textile layer. An example of the multiaxial fiber sheet is “Kuramas” manufactured by Kurashiki Boseki Co., Ltd. As an example, the direction of the multiaxial fiber is 0 ° / + 60 ° / −60 °, the weight per square meter (weight per unit area) is 350 g / m ² , and many PP filaments with a total fineness of 1850 deci tex are used as stitch yarn. There is a multiaxial fiber sheet using polyethylene terephthalate yarn.

  The laminated sheet manufacturing method of the present invention includes, as an example, a polypropylene-based resin sheet transparent layer, a colored layer, and a polypropylene-based resin sheet protective layer that are laminated and integrated in advance, and a core is provided on the surface of the transparent layer via an adhesive film. The layers, the adhesive film on both surfaces, and the fabric layer on both surfaces are heated and pressed, and then cooled. The reason why the polypropylene resin sheet transparent layer, the colored layer, and the polypropylene resin sheet protective layer are laminated and integrated in advance is to improve the efficiency of the final lamination process. The atmospheric temperature in the heating and pressurizing step is preferably 120 to 150 ° C, more preferably 130 to 145 ° C. The applied pressure is preferably about 1 MPa. The heating time is preferably 0.5 to 5 minutes, more preferably 1 to 4 minutes. The time for the cooling step is preferably 0.5 to 5 minutes, and more preferably 1 to 4 minutes. The cooling temperature is preferably about 30 ° C. or less.

  0.5-5 mm is preferable and, as for the thickness of the whole laminated sheet after shaping | molding, More preferably, it is 0.8-4 mm. The range of 0.9 to 1.6 mm is particularly preferable. Within this range, the weight can be reduced and the appearance can be improved. Moreover, it is preferable that the relationship of the layer thickness of a core layer, a textile layer, and a cover layer is core layer> fabric layer> cover layer. This can reduce the weight and improve the appearance.

  The production method of the present invention is not limited to a continuous method, and can be produced by a heating / pressing press and a cooling method for each time. This method is sufficient when producing samples or manufacturing on a small scale. A continuous process is preferred for mass production.

  Next, it demonstrates using drawing. In the following drawings, the same reference numerals indicate the same parts. FIG. 1 is a schematic cross-sectional view of a laminated sheet according to an embodiment of the present invention. In the laminated sheet 8, the fabric layers 3a and 3b are bonded to and integrated with both surfaces of the core layer 1 via the adhesive layers 2a and 2b. A polypropylene-based resin transparent layer 4, a colored layer 5, and a polypropylene-based resin protective layer 6 are laminated and integrated on the surface of the fabric layer 3a via an adhesive layer 2c. Here, the polypropylene resin transparent layer 4, the colored layer 5, and the polypropylene resin protective layer 6 may be laminated and integrated in advance as the cover layer 7.

  FIG. 2 is a schematic cross-sectional view showing the laminated sheet manufacturing apparatus 10 in one embodiment of the present invention. The laminated sheet manufacturing apparatus 10 includes raw material sheet supply rolls 9a to 9g, a heating and pressurizing region 18, and a cooling region 19, and is capable of continuous production. First, the core sheet 11 is supplied from the supply roll 9e, the adhesive films 12a and 12b are supplied from the supply rolls 9d and 9f, the fabrics 13a and 13b are supplied from the supply rolls 9c and 9g, and the adhesive film 12c is supplied from the supply roll 9b. The cover layer sheet 14 is supplied from a supply roll 9a and laminated by pressure rolls 15a and 15b, respectively. Metal pressure plates 16 and 17 are incorporated in the pressure rolls 15a and 15b and 20a and 20b in an endless manner. Next, in the cooling area 19, cooling air is supplied from the arrow a and discharged from the arrow b to be cooled. In the case of efficient cooling, a water cooling pipe is arranged in the cooling region 19 in addition to the cooling air. The laminated sheet 21 taken out from the pressure rolls 20a and 20b is cut into a predetermined length.

  FIG. 3 is a schematic perspective view of a molded body 22 obtained by vacuum forming a laminated sheet according to an embodiment of the present invention. The molded body 22 has a maximum horizontal length of 260 mm, a maximum depth of 170 mm, and a height of 500 mm. The laminated sheet has the advantage that it can be deep drawn. Further, the laminated sheet is entirely made of a thermoplastic resin, and can be subjected to vacuum forming, press forming, bending forming utilizing thermal deformation, and the like, and the forming cycle is short and the processing cost is low. In addition, when the parts are integrated by injection molding with respect to the fabric layer 3b in FIG. 1, the surface of the fabric is an uneven surface, so the injection molded components are easily integrated, and the fabric layer is not deformed by heating, Defects such as sink marks and wrinkles are difficult to enter.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.

<Measurement method of bending elastic modulus and bending stress>
It measured by the 3 point | piece bending test based on JISK7171. The test piece size was 20 mm wide, 50 mm long, and the test speed was 1 mm / min. The shape of the holding jig was R5, the shape of the fulcrum was R2, and the fulcrum interval was 24 mm.

Example 1
<Core layer>
As the core layer 1 shown in FIG. 1, a commercially available propylene-ethylene random copolymer (RPP) sheet, a melting point of 145 ° C., a thickness of 500 μm, and a weight per unit area of 450 g / m ² was used. In the core layer 1, a colorant made of titanium oxide powder was uniformly mixed by 0.1% by weight with respect to 100% by weight of the core layer. The core layer is white and has the same color as the fabric.
<Textile>
As the fabric layers 3a and 3b shown in FIG. 1, a core-sheath composite fiber having a core component made of polypropylene having a melting point of 160 ° C. and a sheath component made of a blend of polypropylene and polyethylene (melting point of 110 ° C.) was used. The composite ratio of the composite fiber was 65% by weight of the core component, 35% by weight of the sheath component, 240 fibers, and the total fineness was 1850 deci tex. This core-sheath composite fiber yarn was fused and used for warp and weft to make a twill-woven fabric. The weight (unit weight) per unit area of the obtained woven fabric was 190 g / m ² .
<Adhesive film>
As the adhesive layers 2a, 2b, and 2c shown in FIG. 1, a commercially available low density polyethylene (LLDPE) film, melting point 110 ° C., thickness 30 μm, and weight per unit area 27 g / m ² were used.
<Cover layer>
As a cover layer 7 shown in FIG. 1, a homopolymer type polypropylene (HPP) sheet 4 having a thickness of 200 μm, a colored layer 5 having a thickness of 1 μm coated with a colored paint, and a homopolymer type polypropylene (HPP) biaxially stretched sheet having a thickness of 25 μm. A cover layer 7 in which 7 was previously laminated and integrated was used.

<Creation of laminated sheet>
The adhesive films 12a and 12b and the fabrics 13a and 13b are laminated on both surfaces of the core sheet 11 shown in FIG. 2, and the adhesive film 12c and the cover layer sheet 14 are laminated in this order on the surface of the fabric 13a, and the temperature is 145 ° C., the pressure is 1 Mpa, It was press-molded for 2 minutes and then cooled to room temperature (27 ° C.). As a result, the adhesive film was welded to integrate the whole to obtain a laminated sheet. A schematic cross-sectional view of this laminated sheet is as shown in FIG.

  Table 1 shows the bending elastic modulus, bending stress, and appearance of the obtained laminated sheet. As for the appearance, “A” indicates that the woven pattern can be expressed without color unevenness by visual observation, and “B” indicates that the back side of the woven side can be seen through and the color unevenness is seen.

(Example 2)
The same operation as in Example 1 was performed except that a homopolymer type polypropylene (HPP) sheet having a melting point of 165 ° C. and a thickness of 200 μm was used as the core layer, and the laminate sheet was press-molded at a temperature of 152 ° C., a pressure of 1 Mpa for 1 minute. . The results of the obtained laminated sheet are summarized in Table 1.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that no colorant was added to the core layer. The results of the obtained laminated sheet are summarized in Table 1. In addition, the data of the bending elastic modulus and bending stress of each example are data of MD (length direction).

  As is apparent from Table 1, the core layer of the example product of the present invention was colored, and the woven pattern of the fabric layer could be expressed beautifully by being colored in the same color as the fabric. Even if there was a part where the woven fabric was slightly transparent, the woven pattern in which the core layer in the back (inner) was colored could be expressed beautifully without uneven color. This laminated sheet was thermoplastic, suitable for vacuum forming, press forming, bending forming utilizing thermal deformation, and the like, and was an inexpensive molded body. Furthermore, since the fabric layer is bonded to the core layer via a heat-sealable polyolefin film, there is no shrinkage of the fibers that make up the fabric even if it is heated and molded later, and the beautiful woven pattern of the fabric remains a laminated sheet. It was possible to obtain a molded body appearing on the surface. In addition, since one side of the laminated sheet is a woven layer, when the rib part is integrated with the woven layer by injection molding, the woven surface is an uneven surface, so the injection molded part is easy to integrate. It was confirmed that defects such as sink marks and wrinkles were difficult to enter.

  On the other hand, since the colorant was not added to the core layer in the product of Comparative Example 1, the laminated sheet was translucent, and when it was formed into a molded body, the back side of the woven pattern portion was transparent, and uneven color was observed. .

  Molded articles using the laminated sheet of the present invention are automobile parts, automobile interior parts, home appliances, medical protective equipment, suitcases, containers, shelves, pallets, panels, bags, sleeve boxes for automatic warehouses, doors, rolls. It can be applied to consumer laminated products such as long boxes, tatami core materials, exhibition booth-like wall materials, T-boards (truck backing plates), and simple table sets.

DESCRIPTION OF SYMBOLS 1 Core layer 2a, 2b, 2c Adhesive layer 3a, 3b Textile layer 4 Transparent layer 5 Colored layer 6 Protective layer 7 Cover layer 8, 21 Laminated sheet 9a-9g Supply roll 10 Laminated sheet manufacturing apparatus 11 Core sheet 12a, 12b, 12c Adhesive films 13a, 13b Fabric 14 Cover layer sheets 15a, 15b, 20a, 20b Pressure rolls 16, 17 Metal pressure plate 18 Heating and pressing area 19 Cooling area 22 Molded body

Claims (14)

A polyolefin-based fiber reinforced resin laminate sheet comprising a fabric layer laminated on both surfaces of the core layer via an adhesive layer,
The core layer is a polypropylene resin containing a colorant,
The woven fabric layer is composed of a yarn including a composite fiber including a first component of polypropylene and a second component of a polyolefin component having a melting point lower than that of the first component;
The adhesive layer is a heat-sealable polyolefin film,
A polyolefin-based fiber-reinforced resin laminate sheet, wherein a cover layer is laminated on one surface of the fabric layer.   The polyolefin fiber-reinforced resin laminated sheet according to claim 1, wherein the cover layer includes a polypropylene resin transparent layer, a colored layer, and a polypropylene resin protective layer.   3. The polyolefin-based fiber reinforced resin laminated sheet according to claim 1, wherein when the core layer is 100% by weight, the colorant is added in an amount of 0.05 to 5.0% by weight.   The polyolefin-based fiber reinforced resin laminate sheet according to any one of claims 1 to 3, wherein the polypropylene-based resin containing a colorant for the core layer is a resin mainly composed of polypropylene or propylene.   The polyolefin fiber reinforced resin laminated sheet according to claim 4, wherein the resin mainly composed of polypropylene of the core layer is a propylene-ethylene random copolymer containing 50 mol% or more of propylene.   The polyolefin fiber reinforced resin laminated sheet according to any one of claims 1 to 5, wherein the composite fiber is a core / sheath composite fiber in which a first component is a core and a second component is a sheath.   The polyolefin fiber-reinforced resin laminated sheet according to claim 6, wherein the core component of the core-sheath composite fiber is a homopolymer polypropylene, and the sheath component is a propylene-ethylene random copolymer or a blend of polypropylene and polyethylene.   The polyolefin fiber-reinforced resin laminated sheet according to any one of claims 1 to 7, wherein the heat-sealable polyolefin film is a low-density polyethylene film.   The polyolefin fiber reinforced resin laminated sheet according to claim 2, wherein the polypropylene resin transparent layer is a blend of a homopolymer type polypropylene and a random type polypropylene.   The polypropylene resin transparent layer has a homopolymer type polypropylene (HPP) and a propylene-ethylene random copolymer (RPP) in a range of HPP: RPP = 50: 50 to 90:10 when the transparent layer is 100% by weight. The polyolefin fiber-reinforced resin laminated sheet according to claim 2, which is a blend of   The polyolefin fiber-reinforced resin laminate sheet according to claim 2, wherein the protective layer is a biaxially stretched polypropylene resin sheet.   The polyolefin fiber reinforced resin laminate sheet according to any one of claims 1 to 11, wherein the total thickness of the polyolefin fiber reinforced resin laminate sheet is in a range of 0.9 to 1.6 mm.   The polyolefin-based fiber-reinforced resin laminate sheet according to any one of claims 1 to 12, wherein a relationship among layer thicknesses of the core layer, the fabric layer, and the cover layer is core layer> fabric layer> cover layer. A method for producing a polyolefin-based fiber reinforced resin laminate sheet according to any one of claims 1 to 13,
A method for producing a polyolefin-based fiber reinforced resin laminated sheet, comprising: a cover layer sheet; and a fabric sheet disposed on both surfaces of the core sheet via an adhesive film, heated and pressurized, and then cooled.

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